Electronic Supplementary Material One-pot synthesis of MoSe 2 hetero-dimensional hybrid self-assembled by nanodots and nanosheets for electrocatalytic hydrogen evolution and photothermal therapy Baoguang Mao 1,2, Tao Bao 3, Jie Yu 3, Lirong Zheng 4, Jinwen Qin 1,2, Wenyan Yin 3 ( ), and Minhua Cao 1,2 ( ) 1 Key Laboratory of Cluster Science, Ministry of Education of China, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China 2 Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China 3 CAS Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China 4 Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China Supporting information to DOI 10.1007/s12274-017-1469-7 S1 Supporting discussion S1.1 Measurement and calculation of photothermal performance To examine the photothermal properties of MoSe 2 HDH, different concentrations of MoSe 2 HDH dispersed in water were irradiated by a NIR laser (808 nm, 1 W/cm 2 ) for 600 s in a 1 cm square cuvette. The temperature trends of all samples were measured by an IR thermal imaging system. Photothermal effect of distilled water as the control group was evaluated with the same parameters as the tested group. To further investigate the photothermal conversion efficiency of MoSe 2 HDH, the aqueous dispersion (25 ppm) was irradiated with 808 nm NIR laser (1 W/cm 2 ) for 600 s and the laser was shut off. The photothermal conversion efficiency (η) was calculated as follows hs( T T ) Q I max surr 0 A808 (1 10 ) Where h is the heat transfer coefficient, I is the laser power, S is the surface area of the container, T max is the steady state maximum temperature, T surr is the ambient temperature of the surroundings, heat energy Q 0 is the heat associated with the light absorbance of the solvent, and A 808 is the absorbance of MoSe 2 HDH dispersion at 808 nm. The detailed information for the calculations of hs and Q 0 is similar to our previous reports [S1, S2]. Finally, the NIR 808 nm laser-induced photothermal conversion efficiency η of the sample was calculated to be 48.46%. Address correspondence to Minhua Cao, caomh@bit.edu.cn; Wenyan Yin, yinwy@ihep.ac.cn
Nano Res. S2 Supplementary figures Figure S1 (a) XRD pattern and ((b) and (c)) TEM images of MoSe2 NSs prepared in the absence of PEG 400. The inset in (b) shows the corresponding SAED pattern. Figure S2 SAED pattern taken on a typical MoSe2 HDH, corresponding to the TEM image in Fig. 1(c). Figure S3 (a) and (b) AFM images of MoSe2 HDH with different magnifications. (c) Corresponding height profile of the surface MoSe2 NDs. www.editorialmanager.com/nare/default.asp
Figure S4 ((a) and (b)) TEM images of MoSe 2 NDs with the size of ca.10 nm formed through the bath sonication process. (c) TEM image of MoSe 2 NDs & NSs. Figure S5 The extrapolation method for the exchange current densities of MoSe 2 HDH, MoSe 2 NDs & NSs, MoSe 2 NSs, MoSe 2 NDs and Pt/C. Figure S6 The Nyquist plots of MoSe 2 HDH at different overpotentials. www.thenanoresearch.com www.springer.com/journal/12274 Nano Research
Figure S7 Cyclic voltammograms at different scan rates in the region of 260 360 mv vs. RHE in 0.5 M H 2 SO 4 : (a) MoSe 2 NDs & NSs, (b) MoSe 2 NDs, and (c) MoSe 2 NSs. Figure S8 (a) UV vis NIR absorption spectrum of MoSe 2 NSs. (b) Temperature increase of MoSe 2 NSs dispersions as a function of irradiation time (600 s). (c) Photothermal response of MoSe 2 NSs dispersion (50 ppm) for 600 s with the NIR 808 nm laser (1 W/cm 2 ). The laser was shut off after irradiation for 600 s. (d) Plot of cooling period of (c) vs. negative natural logarithm ( ln θ) of driving force temperature. Figure S9 Body weight of mice from the control group and MoSe 2 HDH group, respectively. www.editorialmanager.com/nare/default.asp
Figure S10 Photo of the as-prepared MoSe 2 HDH dispersed in deionized water for more than 30 days. The concentration is ca. 1.0 mg/ml. Figure S11 (a) Fourier transform infrared (FT IR) spectra of the purified MoSe 2 HDH, MoSe 2 HDH and pure PEG 400. The C H and C O C groups remain on the surface of the MoSe 2 HDH, which result from the PEG 400. The purified MoSe 2 HDH was obtained after a surfactant removal process from the MoSe 2 HDH. (b) Thermal gravimetric (TGA) analysis of the MoSe 2 HDH in nitrogen atmosphere. The weight loss region (250 550 C) should be attributed to the decomposition of PEG 400. The amount of PEG 400 was determined to be ca. 45 wt.%, indicating that PEG 400 was adsorbed on the surface of the MoSe 2 HDH. Table S1 Hematology analysis and blood biochemical assay Mouse CREA (μmol/l) UREA (mmol/l) CK (U/L) ALT (U/L) AST (U/L) Control 1 61.4 6.62 1,032.5 46.6 112.3 Control 2 62.5 6.01 1,011.7 47.8 100.4 Control 3 59.1 7.33 994 42.9 108.1 Test 1 75.2 4.94 1,873.5 54.0 178.5 Test 2 70.8 9.18 813.2 58.0 232.0 Test 3 65.5 7.18 917.5 51.3 228.5 www.thenanoresearch.com www.springer.com/journal/12274 Nano Research
Table S2 Routine blood test analysis of mice administrated with the MoSe 2 HDH Test Unit Control group Test group WBC 10 9 /L 8.12 ± 0.41 7.90 ± 1.74 RBC 10 12 /L 7.51 ± 0.25 8.66 ± 0.32 HGB g/l 15.65 ± 2.62 16.65 ± 1.52 HCT % 45.8 ± 0.68 47.08 ± 1.63 MCV fl 49.75 ± 1.67 53.31 ± 0.12 MCH pg 19.43 ± 0.5 18.62 ± 1.61 MCHC g/l 34.54 ± 0.43 35.4 ± 0.53 PLT 10 9 /L 374.3 ± 21.7 405.8 ± 22.4 PCT % 0.32 ± 0.05 0.33 ± 0.04 RDW % 14.65 ± 0.15 14.74 ± 0.12 MPV fl 4.04 ± 0.04 3.78 ± 0.1 PDW % 17.86 ± 0.31 15.65 ± 0.75 LYM 10 9 /L 3.65 ± 0.05 3.32 ± 0.76 MID 10 9 /L 1.0 ± 0.07 0.9 ± 0.21 GRN 10 9 /L 2.6 ± 0.14 2.51 ± 0.14 LYM% % 58.74 ± 1.5 60.75 ± 2.61 MID% % 12.54 ± 0.72 12.88 ± 0.07 GRN% % 37.1 ± 6.7 37.69 ± 4.67 EOS 10 9 /L <0.7 <0.7 References [S1] Yin, W.; Yan, L.; Yu, J.; Tian, G.; Zhou, L.; Zheng, X.; Zhang, X.; Yong, Y.; Li, J.; Gu, Z.; Zhao, Y. et al. High-throughput synthesis of single-layer MoS 2 nanosheets as a near-infrared photothermal-triggered drug delivery for effective cancer therapy. ACS Nano 2014, 8, 6922 6933. [S2] Liu, J.; Zheng, X.; Yan, L.; Zhou, L.; Tian, G.; Yin, W.; Wang, L.; Liu, Y.; Hu, Z.; Gu, Z. et al. Bismuth sulfide nanorods as a precision nanomedicine for in vivo multimodal imaging-guided photothermal therapy of tumor. ACS Nano 2015, 9, 696 707. www.editorialmanager.com/nare/default.asp